Textile treating dispersions



v ment and storage.

United States PatentO 2,972,548 TEXTILE TREATING DISPERSIONS David M. Musser, Fairlawn, N.J., assignor, by mesue assignments, to Chicopee Manufacturing Corporation, New Brunswick, N.J., a corporation of Massachusetts No Drawing. Filed Oct. 17, 1957, Ser. No. 690,624 5 Claims. (Cl. 106-287) This invention relates to aqueous colloidal dispersions which are adapted for use in the treatment of textiles to render them non-wettable, and to the method for the production of such dispersions. More particularly, this invention relates to stable aqueous dispersions of methylene aliphatic diamides, in which the aliphatic group is a relatively long hydrocarbon chain and to a method for their production.

The experimental treatment of 'a textile fabric with methylene distearamide for the purpose of rendering the fabric water repellent has heretofore been reported in the literature. The diamide was applied to the fabric as a solution in glacial acetic acid. A glacial acetic acid solution, rather than an aqueous dispersion was used for this purpose, for the stated reason that the diamide was found to be difiicult, if not impossible, to disperse in Water as a colloidal dispersion.

This treatment is wholly impractical for commercial use because of the requirement for the use of glacial acetic acid as a solvent. The glacial acetic acid solution must be applied while quite warm and is thus extremely difiicult to handle. Furthermore, the water repellent finish resulting from this treatment was unsatisfactory, since it was entirely destroyed by four to six launderings, and, therefore, was not competitive with the finishes produced by the use of commercial materials using stearamidomethylpyridinium chloride as an active ingredient which are available for this purpose.

It is one of the objects of this invention to provide a method for the production of an aqueous colloidal dispersion of a methylene aliphatic diamide, in which the aliphatic groups are relatively long carbon chains, which is stable and adapted for use as an active ingredient in admixture, with other materials in textile treating baths for the production of water repellent finishes.

Another object of this invention is to provrde a stable aqueous dispersion of a methylene diamide of relatively high, molecular weight which can be shipped and stored without separation of its phases, and which is freely misci-- ble with other aqueous dispersions and water soluble materials used in textile treating baths, even after ship- Other objects of this invention and its various advantageous features will become readily apparent as this By carrying out the reaction for the formation of the methylene diamide in this manner, the product is suspended in the aqueous reaction rnedium as it is formed, instead of forming a gummy unmanageable precipitate which is difficult, if.

2,972,548 Patented Feb. 21, 1961 not impossible, to suspend as a colloid. The reaction mixture which I obtain in this manner is readily reduced to a true colloidal suspension, which can be used as an active ingredient in the formulation of textile treating baths intended for the production of nonwettable finishes, without further processing.

By the method, in accordance with this invention, a long chain aliphatic amide having the generic formula RCONH in which R represents an aliphatic hydrocarbon chain of 16 to 30 carbon atoms, such as, for example, octadecyl amide (or stearyl amide), oleyl amide, montan amide, etc., is reacted with formaldehyde. This reaction is carried out in an aqueous reaction medium, which has dissolved therein one or more surface active agents. The surface active agent or agents utilized in this reaction mixture must be stable under the conditions required for the reaction and must not themselves enter into the reaction.

I have found that the amount of emulsifier present in the reaction mix has an effect on the reaction. If too large an amount is added the reaction is incomplete and a low yield of the desired product is obtained. If the amount is insufiicient, the product will not be emulsified and the product will flocculate and precipitate as a gummy mass. The optimum amount is readily deter- 'mined by observation and by the proportions set out hereafter.

While I do not want to be bound by any theories regarding the reactions taking place, it is .my belief that the chemical reaction involved here takes place in two steps. In the first step formaldehyde is believed to react with the long chain aliphatic amide to form a methylol derivative according to the following equation:

In the second step, this methylol derivative is believed to react, when under acid conditions, with an additional quantity of aliphatic amide toform the diamide, accordaction of octadecyl amide (stearyl amide) with formaldehyde results in a product which as the following structural formula:

H 17 a5-'( 3N V cm O1 H3 -CN o H This compound is alternatively known as methylene distearamide or as distearamide methane.

- agent as a reaction medium, in two stages. 'stage of the reaction is carried out under substantially -tween about 2.0-to about 3.0.

condition by-the addition of, for example, hydrochloric Regardless of the theories involved, I carry out'the reaction, utilizing an aqueous solution of a surface active The first non-acidic conditions. The second stage of the reaction is carried out under definitely acid conditions, for example,

in an aqueous reaction medium having a pH within the range of about 1.0 to about 4.0, preferably however be- I provide such an acid acid, tothe aqueous reaction medium after the first stage of the reaction has been completed, andthen continue the reaction through the second stage.

Since the second stage of this reaction is carried out under acid conditions, the surface active agent or agents which I use in the aqueous reaction medium must be stable and retain surface activity in acid solution. Although this requirement excludes some of the more commen anionic surface active agents, such as, for example, the ordinary soaps, there are a Wide variety of surface active agents now commercially available which are adapted for use in acid media and which are well suited for use in my method. Thus, for example, my work has led me to the conclusion that any of the hundreds of non-ionic surface active agents now available are suitable for this purpose. I have found that sorbitan monopalmitate or glycerol monopalmitate either alone or in admixture with polyoxyethylene sorbitan monopalmitate are entirely satisfactory for my purpose. The aqueous solution of the surface active agent which I use as my reaction medium may contain an amount of surface active agent within the range of about 1 part by weight to about 5 parts by weight for each 100 parts by weight of the reaction mixture.

At the completion of the two steps of this reaction, the product is suspended in the aqueous reacted mixture, instead of being in the form of a gummy precipitate. This suspended product is relatively concentrated and rather unstable. Additional emulsifier is added at this point in the form of aqueous solutions to both dilute the product and render it stable to subsequent treatment. This aqueous suspension of the product is then subjected to vigorous agitation, passed through a colloid mill or through a homogenizer to reduce all the suspended particles therein to a particle size within the colloidal range, and produce a colloidal suspension which does not separate on shipment and storage, and which is readily miscible with other aqueous dispersions and with mater-miscible materials used in the treatment of textiles.

Thus, it will be understood that the product, in accordance with this invention, is a colloidal suspension of a compound having the generic formula (RCONH) CH in which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms, and which may be termed a methylene di-aliphatic amide, or a di-aliphatic amide methane, in an aqueous solution of a surface active agent which is stable in acid solution.

In producing this colloidal suspension, I have found that the proportion of the long chain aliphatic amide in the initial reaction mixture may vary between about 8% by weight to about 30% by weight of the total reaction mixture. A smaller proportion of the amide in the reaction mixture leads to ineflicient operation, while percentages above this range results in a final reacted mixture in which the methylene di-aliphatic amide is not properly suspended.

According to the theory of the reaction utilized here, which has been mentioned hereinbefore, one mole of formaldehyde is theoretically required to convert two moles of the aliphatic amide to methylene di-aliphatic amide. I prefer to use stoichiometric ratio of about 0.7 mole to about 2.0 mole of formaldehyde per mole of long chain aliphatic amide contained in the reaction mixture. As an alternative to the use of formaldehyde itself in the reaction mixture, I may use any formaldehyde yielding compounds, such as, paraformaldehyde or glyoxal in the reaction mixture.

In carrying out this reaction, I prefer to use a relatively concentrated mixture to obtain efficiency in the reaction and produce a reacted mixture which is acid in reaction. As a matter of operating procedure, I prefer to neutralize the acid in the reacted mixture by the addition of a base such as an alkali metal hydroxide, for example, sodium hydroxide, potassium hydroxide, etc., ammonium hydroxide, a basic salt such as sodium carbonate or sodium bicarbonate, or an organic base, such as monoethanolamine, at the end of the reaction.

The reaction mixture contains a greater amount of the aqueous solution of the surface active agent than is ordinarily desirable in the final colloidal product. Therefore, after the completion of the reaction and either before or after the neutralization of the acid contained in the reacted mixture, 1 dilute the mixture with water or an additional quantity of an aqueous solution of a surface active agent to give a standardized product. The aqueous solution of a surface active agent which I may use for this dilution of the reacted mixture may be the same or different from that used as the reaction medium. In the alternative in which I neutralize the acid in the reacted mixture prior to the dilution step, I may use a surface active agent in the dilution step which is sensitive to acid. In this dilution step, for each parts of the aqueous solution of a surface active agent which I use as a reaction medium, I may add an additional quantity of such a solution within the range of about 2 parts to about 4 parts by weight. I prefer to carry out this dilution step before the reaction mixture is subjected to agitation, the action of colloid mill or of a homogenizer to reduce the suspended particles of the methylene dialiphatic amide to the colloidal range.

The following examples illustrate the method and product, in accordance with this invention, but it will be understood that the invention is not limited to these examples, which are chosen solely for the purpose of illustration.

EXAMPLE I A mixture of the following ingredients were mixed together and refluxed for a period of one hour at a temperature of 96 90 C.:

Parts by weight *Octadecylamide 14.5

Formaldehyde, 37% aqueous solution 5.8 Sorbitan monopalmitate 0.5 Polyoxyethylene sorbitan monopalmitate 0.5 Water 60.0

reaction mixture:

Parts by weight sorbitan monopalmitate 1.5 Polyethylene sorbitan monopalmitate 1.5 Water 14.7

This mixture was then vigorously stirred and homogenized to produce a uniform, stable dispersion in which methylene distearamide is the disperse phase and an aqueous solution of sorbitan monopalmitate and polyoxyethylene sorbitan monopalmitate is the continus phase.

EXAMPLE II Methylene distearamide emulsion preparation A mixture of the following ingredients were refluxed for of an hour at a temperature of -200 F.:

Parts by weight Octadecylamide 22 Formaldehyde (37% solution) 9 Sorbi-tan monopalmitate 1 Water 52 After this period of reflux, 5 parts by weight of dipropylene glycol was added to the reaction mixture and its pH was adjusted to a value within the range of about 1 to about 4 preferably between 2.0 to 3.0 by the addition of 20 Baum hydrochloric acid. The dipropylene glycol was added to keep the emulsion smooth; it also has foam suppressant properties. The resulting mixture was then heated at 184-.188.F. for a period of one .hour. The

reaction mixture was then neutralized by the addition of monoethanolamine, and then cooled, while stirring to a temperature of 150 F. An aqueous solution having the following composition was then added to the reaction mixture:

Parts by weigh Sorbitan monopalmitate 3.5 Mineral oil 2.0 'Water 5.5

This'mixture was then passed through a colloid mill.

The mineral oil has been found advantageous in that it appears both to aid in the emulsification of the other ingredients and to suppress any tendency of the composition to foam. Other ingredients which answer the same purpose may be added in place of the mineral oil, such as dipropylene glycol.

In the foregoing, I have referred to the product, in accordance with this invention, as an aqueous colloidal suspension. since the suspended long chain diamides melt above normal temperatures and the suspended particles are undoubtedly in the solid phase at normal room temperatures. This terminology is not used by way of limitation of my invention and it may be noted that such suspensions are frequently referred to as emulsions in the textile industry.

While I have specifically exemplified the method and product, in accordance with this invention, and have given various alternatives both as to materials and as to reaction conditions and treatments, it will be understood that these are for illustrative purposes only and that various modifications and changes can be made as to the reaction conditions, materials, etc., without departing from the spirit of my invention or the scope of the following claims.

I claim:

1. The method for the production of an aqueous colloidal dispersion which comprises heating a compound having the formula RCONH in which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms with formaldehyde, in a reaction medium comprising an aqueous solution containing about 1 part to about 5 parts per 100 parts by weight of said reaction medium of an acid-stable non-ionic surface active agent to produce a compound having the generic formula RCONHCH OH in which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms and then causing this compound to react with an additional amount of the said RCONH compound by lowering the pH of said reaction medium to between about 1 and about 4 and heating to produce a compound having the generic formula ncounu cn with formaldehyde in a reaction medium comprising an aqueous solution containing about 1 part to about 5 parts per parts by weight of said reaction medium of an acid-stable non-ionic surface active agent to produce methylol steararnide and then causing this compound to react with additional octadecylarnide by lowering the pH of said reaction medium to between about 1 and about 4 and heating to produce methylene distearamide in suspension in the said reaction medium and thereafter adding a further amount of an acid-stable non-ionic surface active agent, neutralizing the acid in the reaction mixture by the addition of a base and mechanically treating the reaction mixture to reduce the suspended compound to particles of colloidal size.

3. The method for the production of an aqueous colloidal dispersion which comprises refluxing octadecylamide with formaldehyde in a nonacidic reaction medium comprising an aqueous solution containing about 1 part to about 5 parts per 100 parts by weight of said reaction medium of an acid-stable non-ionic surface active agent to produce methylol stearamide and then adding acid tothe reaction to reduce its pH to the range of about 2.0 to about 3.0 and heating to cause the methylol stearamide to react with octadecylamide to produce methylene distearamide in suspension in the said reaction medium, neutralizing the acid in the reaction mixture by the addition of a base, and thereafter adding a surface active agent and treating the reaction mixture to reduce the suspended compound to particles of colloidal size.

4. The method for the production of an aqueous colloidal dispersion which comprises refluxing from 8% to 40% by weight of the total reaction mixture of octadecylamide with about 0.7 mol to 2.0 mols of formaldehyde per mol of amide in a non-acidic reaction medium comprising an aqueous solution containing about 1 part to about 5 parts per 100 parts by weight of said reaction medium of an acid-stable non-ionic surface active agent to produce methylol stearamide and then adding acid to the reaction to reduce'its pH to the range of about 2.0 to about 3.0 and heating to cause the methylol steararnide to react with octadecylamide to produce methylene distearamide in suspension in the said reaction medium, neutralizing the acid in the reaction mixture by the addition of a base, diluting the reaction mixture by the addition of an aqueous solution of a surface active agent thereto and thereafter treating the reaction mixture to reduce the suspended compound to particles of colloidal size.

5. An aqueous stable colloidal dispersion consisting of a continuous phase comprising a solution of about 1 part to about 5 parts per 100 parts by weight of said colloidal dispersion of an acid-stable non-ionic surface active agent in water and a discontinuous phase comprising colloidal particles of acornpound produced in situ having the formula (RCONH) CH in which R represents an aliphatic hydrocarbon chain containing 16 to 30 carbon atoms.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Atlas Spans and Tweens" (1943), pp. 2, 8 and 13.

UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTION Patent Now 2,972,548 February 21, 1961 David M Musser It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. 7

Column 4, line 15, after "of", first occgrregl'ce, insert a line 27, for "%-9o 0.1 read 96 -99 c.

line 36; for ".coolde'"; read cooled line 56 for "continus" read continuo.us-; column 5, line 60 for "paritcles" read particles.

Signed and sealed this 8th day of August 1961.

SEAL) fittest:

ERNEST SWIDER I DAVID L. LADD Attesting Officer Commissioner of Patents 

1. THE METHOD FOR THE PRODUCTION OF AN AQUEOUS COLLOIDAL DISPERSION WHICH COMPRISES HEATING A COMPOUND HAVING THE FORMULA RCONH2 IN WHICH R REPRESENTS AN ALIPHATIC HYDROCARBON CHAIN CONTAINING 16 TO 30 CARBON ATOMS WITH FORMALDEHYDE, IN A REACTION MEDIUM COMPRISING AN AQUEOUS SOLUTION CONTAINING ABOUT 1 PART TO ABOUT 5 PARTS PER 100 PARTS BY WEIGHT OF SAID REACTION MEDIUM OF AN ACID-STABLE NON-IONIC SURFACE ACTIVE AGENT TO PRODUCE A COMPOUND HAVING THE GENERIC FORMULA 